ZrO2-Al2O3 composite ceramic material

ABSTRACT

A ZrO 2 —Al 2 O 3  composite ceramic material is provided, which is excellent in mechanical strength and toughness, and has the capability of preventing low temperature degradation. This ceramic material includes a first phase of ZrO 2  grains having an average grain size of 0.1 to 0.8 μm, and containing 10 to 12 mol % of CeO 2  and 0.005 mol % to less than 0.5 mol % of Y 2 O 3 , and a second phase of Al 2 O 3  grains having an average grain size of 0.1 to 0.5 μm. The ZrO 2  grains is composed of 90 vol % or more of tetragonal ZrO 2 , and a content of the second phase in the composite ceramic material is in a range of 20 to 60 vol %, and preferably 30 to 50 vol %.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a ZrO₂—Al₂O₃ composite ceramic material having excellent mechanical properties and the capability of preventing low temperature degradation.

2. Disclosure of the Prior Art

In contrast to typical ceramic materials such as alumina, silicon nitride and silicon carbide, yttria-stabilized tetragonal zirconia polycrystals (Y-TZP) containing 2 to 3 mol % of Y₂O₃ as a stabilizer demonstrate excellent mechanical properties, e.g., high strength and high toughness, and therefore is already widely in practical use. In recent years, the Y-TZP ceramic is beginning to be applied as a biomaterial for artificial joints, artificial tooth roots, abutment, crown and so on.

However, the Y-TZP ceramic has a problem that a phase transformation from metastable tetragonal ZrO₂ to monoclinic ZrO₂ proceeds at a relatively low temperature region, e.g., 200 to 300° C., while accompanying a volume expansion of about 4.6%. Due to microcracks developed in the Y-TZP ceramic by this volume expansion, a considerable deterioration in mechanical properties occurs. In addition, it is well known that the phase transformation is further accelerated under a wet condition (e.g., in vivo environments). As one of major causes for such a low temperature degradation of the Y-TZP ceramic, it is believed that trivalent yttrium ions are interstitially dissolved in eight-coordinate positions of tetravalent zirconium ions, so that oxygen defects are generated in ZrO₂ lattice by the difference in valence level.

On the other hand, ceria-stabilized tetragonal zirconia polycrystals (Ce-TZP) containing CeO₂ as the stabilizer are also widely known. In this case, since tetravalent cerium ions are dissolved into the ZrO₂ lattice, the oxygen defects are not generated. It has been supported by lots of experimental data that the low temperature degradation of the Ce-TZP ceramic does not happen crystallographically. In addition, this ceramic demonstrates a remarkably high toughness. However, there is a problem that the mechanical strength and hardness of the Ce-TZP ceramic are much lower than those of the Y-TZP ceramic. Consequently, it has been a significant barrier to the practical use.

For example, as disclosed in Japanese Patent Early Publication No. 63-156063 or No. 63-123861, both of ceria and yttria is used as the stabilizer to obtain a high-strength ZrO₂ sintered body. This ZrO₂ sintered body includes a partially stabilized zirconia mainly composed of tetragonal ZrO₂ or tetragonal ZrO₂ and cubic ZrO₂, which contains 4 to 6 mol % of ceria (CeO₂) and 2 to 6 mol % of yttria (YO_(1.5)) as the stabilizer, and a second phase of at least one selected from alumina, spinel and mullite. In this case, it is believed that thermal stability is improved because ZrO₂ of this sintered body has a structure closer to a cubic crystal that is the high-temperature stable phase of ZrO₂, as compared with the tetragonal ZrO₂ containing only yttria as the stabilizer.

However, there is another problem that, during sintering, crystal grains of the cubic ZrO₂ easily become larger in size than the case of the tetragonal ZrO₂. That is, abnormal grain growth of ZrO₂ easily occurs. Therefore, it is difficult to ensure sufficient strength, hardness and wear resistance with reliability. In addition, the presence of the second phase such as alumina and mullite makes difficult to complete the sintering of ZrO₂ matrix containing yttria as the stabilizer. As a result, a specialized sintering technique such as pressure sintering or HIP will be needed to obtain a dense sintered body. This leads to an increase in production cost and restricts the production of a sintered body having a complex shape.

SUMMARY OF THE INVENTION

Therefore, a concern of the present invention is to provide a ZrO₂—Al₂O₃ composite ceramic material, which is excellent in mechanical strength and toughness, and has the capability of substantially conquering the problem of low temperature degradation.

That is, the ceramic material of the present invention comprises a first phase of ZrO₂ grains having an average grain size of 0.1 to 0.8 μm, and containing 10 to 12 mol % of CeO₂ and 0.005 mol % to less than 0.5 mol % of Y₂O₃, and a second phase of Al₂O₃ grains having an average grain size of 0.1 to 0.5 μm. The ZrO₂ grains are composed of 90 vol % or more of tetragonal ZrO₂, and a content of the second phase in the composite ceramic material is in a range of 20 to 60 vol %.

In general, it is said that 2 to 3 mol % of Y₂O₃ is needed as the stabilizer for tetragonal ZrO₂. In contrast thereto, the present invention is essential to use a required amount of CeO₂ as the stabilizer in combination with an extremely small amount of Y₂O₃. In this case, it is interesting to note that the stabilizer function is hardly expected by the addition of Y₂O₃. That is, one of important findings in the present invention is in that the use of 10 to 12 mol % of CeO₂ as the stabilizer in combination with 0.005 to less than 0.5 mol % of Y₂O₃ is effective to remarkably improve poor mechanical properties that are major disadvantages of the Ce-TZP ceramic, and simultaneously prevent the low temperature degradation that is a major disadvantage of the Y-TZP ceramic. Thus, the technical concept of the present invention is different from the conventional technical concept of improving thermal stability of the Y-TZP ceramic by using both of CeO₂ and Y₂O₃ as the stabilizer.

These and still other objects and advantages of the present invention will become more apparent from the detail description of the invention and preferred examples explained below.

DETAIL DESCRIPTION OF THE INVENTION

A ZrO₂—Al₂O₃ composite ceramic material of the present invention and a production method thereof are explained in detail below.

The ZrO₂—Al₂O₃ composite ceramic material of the present invention is essential to use ZrO₂ grains containing 10 to 12 mol % of CeO₂ and 0.005 mol % to less than 0.5 mol % of Y₂O₃ as the first phase. As described before, CeO₂ plays an important role as the stabilizer for tetragonal ZrO₂ with the capability of preventing the low temperature degradation. When the CeO₂ content is in the range of 10 to 12 mol %, the ZrO₂ grains of the first phase is composed of 90 vol % or more of tetragonal ZrO₂. Even when monoclinic ZrO₂ appears in the first phase, its content is less than 10 vol %. At this time, there is no generation of cubic ZrO₂. Therefore, mechanical strength and toughness can be effectively improved according to the stress-induced phase transformation effect of ZrO₂. On the other hand, when the CeO₂ content is less than 10 mol %, the amount of monoclinic ZrO₂ relatively increases, so that microcracks easily develop in the composite ceramic material. This leads to a considerable decrease in mechanical strength. When the CeO₂ content is more than 12 mol %, the cubic ZrO₂ of the high-temperature stable phase begins to appear in the composite ceramic material. When the amount of tetragonal ZrO₂ becomes less than 90 vol % due to the generation of the cubic ZrO₂, sufficient mechanical strength and toughness can not be obtained.

By the way, it is already known that 2 to 3 mol % of Y₂O₃ is used as the stabilizer for tetragonal ZrO₂. On the other hand, the present invention is essential to use an extremely small, limited range, i.e., 0.005 to less than 0.5 mol %, of Y₂O₃ with respect to the total amount of ZrO₂. Therefore, in the present invention, the stabilizer effect of Y₂O₃ can not be expected. In other words, when less than 0.5 mol % of Y₂O₃ is added to ZrO₂ by itself, the monoclinic ZrO₂ becomes dominant. Thus, the stabilizer effect can not be obtained by use of the small amount of Y₂O₃.

However, the present inventors found that by using 10 to 12 mol % of CeO₂ in combination with the small amount of Y₂O₃, both of the problem of low temperature degradation that is a disadvantage of the Y-TZP ceramic and the problem of poor mechanical strength that is a disadvantage of the Ce-TZP ceramic can be solved simultaneously. In the present invention, when the content of Y₂O₃ is less than 0.005 mol %, the effect of inhibiting abnormal grain growth of ZrO₂ becomes insufficient, so that improvements of the mechanical strength and hardness of the composite ceramic material can not be achieved. On the other hand, when the content of Y₂O₃ is larger than 0.5 mol %, the stabilizer effect of Y₂O₃ gradually begins to appear. It means that the low temperature degradation becomes a problem.

In the case of using CeO₂ as the stabilizer for tetragonal ZrO₂ in combination with the small amount of Y₂O₃, without wishing to be bound by theory, it is believed that an inhibiting mechanism of abnormal grain growth described below play an important role to improve the mechanical properties of the ZrO₂—Al₂O₃ composite ceramic material.

That is, Chen et al (S. L. Hwang and I-W Chen J. Am. Ceram. Soc., 73, 3269 (1990)) reported that effects of various dopants on the grain growth of ceria stabilized tetragonal ZrO₂ grains were investigated, and as the dopant has a smaller valence level than Ce⁴⁺, the inhibition of grain growth increases. In addition, it was reported that when the dopant has the same valence level as Ce⁴⁺, the inhibition of grain growth is further increased by the dopant having a larger ionic radius than Ce⁴⁺. Therefore, it is believed that the effect of grain-growth inhibition, observed in the present invention, is caused by the presence of Y³⁺ having a smaller valence level than Ce⁴⁺, and a larger ionic radius (1.019×10⁻¹ nm) than Ce⁴⁺(0.97×10⁻¹ nm).

Moreover, Ikuhara et al (Y. Ikuhara, T. Sakuma, Ceramics, 32, 524 (1997)) reported that a localized composition analysis for grain boundary of a Y-TZP ceramic having a stable grain-boundary structure and a uniform grain-size distribution was performed, and segregation of yttrium (Y) was observed at a region having a width of several nanometers in the vicinity of the grain boundary. As in the case of the Y-TZP ceramic, there is a possibility that a similar segregation of Yttrium in the vicinity of grain boundary happens in the Ce-TZP ceramic. It is believed that the occurrence of such a segregation in the vicinity of grain boundary lowers the mobility of grain boundary and enhances the effect of grain growth inhibition.

In the present invention, the ZrO₂ grains of the first phase have an average grain size of 0.1 to 0.8 μm. When the average grain size is more than 0.8 μm, it leads to reductions in mechanical strength and wear resistance of the composite ceramic material or variations in mechanical properties. On the other hand, it is difficult to realize the first phase having the average grain size of less than 0.1 μm in the composite ceramic material. In particular, since pressure sintering or HIP treatment is needed to obtain a dense sintered body, a deterioration of cost performance and a decrease in production yield come into problems. In addition, it becomes difficult to disperse fine Al₂O₃ grains efficiently within the ZrO₂ grains in order to form a “nano composite structure” described later in the composite ceramic material of the present invention.

In the present invention, it is also preferred that a ratio of the number of the ZrO₂ grains that are two or more times larger than the average grain size of the first phase relative to the number of the entire ZrO₂ grains dispersed in the composite ceramic material is 10% or less. This ratio can be achieved by use of the above-defined amounts of CeO₂ and Y₂O₃. If necessary, the first phase may further contain titania, magnesia, calcia or a small amount of impurities.

In addition, the second phase of the ZrO₂—Al₂O₃ composite ceramic material of the present invention is essentially composed of Al₂O₃ grains having an average grain size of 0.1 to 0.5 μm. When the average grain size is less than 0.1 μm, aggregation of the Al₂O₃ grains begins to appear, and it becomes difficult to distribute the Al₂O₃ grains uniformly in the first phase. It leads to variations in mechanical properties. On the other hand, when the average grain size is more than 0.5 μm, wear resistance and hardness of the ceramic composite material decrease. In particular, since the Al₂O₃ grains can not be dispersed efficiently within the ZrO₂ grains of the first phase, it becomes difficult to form the “nano composite structure” described above in the composite ceramic material.

In addition, the composite ceramic material of the present invention is essential to contain 20 to 60 vol %, and preferably 30 to 50 vol % of Al₂O₃ grains. When the Al₂O₃ content is less than 20 vol %, the mechanical strength and the wear resistance of the composite ceramic material can not be sufficiently improved. Moreover, the ratio of the number of the ZrO₂ grains that are two or more times larger than the average grain size of the first phase relative to the number of the entire ZrO₂ grains dispersed in the composite ceramic material easily becomes more than 10%. On the other hand, as the Al₂O₃ content exceeds 50 vol %, the mechanical strength gradually decreases due to an increase in aggregation of Al₂O₃ grains. When the Al₂O₃ content is more than 60 vol %, a considerable decrease in mechanical strength and toughness occurs because the matrix phase is composed of Al₂O₃. When the composite ceramic material contains 30 to 50 vol % of the second phase, it is possible to provide the ceramic composite material having well-balanced mechanical strength and toughness in higher levels.

In the present invention, it is preferred that a fine Al₂O₃ grains are dispersed within the ZrO₂ grains to form the “nano composite structure in the composite ceramic material. To obtain the “nano-composite structure”, an appropriate degree of grain growth of the ZrO₂ grains is needed. However, the excessive grain growth causes deteriorations in mechanical strength, hardness and wear resistance. In the present invention, the appropriate degree of grain growth of the ZrO₂ grains can be achieved by use of the above-defined amounts of CeO₂ and Y₂O₃. In this case, it is also preferred that a ratio of the number of the Al₂O₃ grains dispersed within the ZrO₂ grains relative to the number of the entire Al₂O₃ grains dispersed in the composite ceramic material is 2% or more.

Advantages brought by the induction of the “nano-composite structure” into the composite ceramic material are briefly explained. First, the ZrO₂ grains of the first phase can be remarkably reinforced by the formation of the “nano-composite” structure. In addition, the uniform of the fine structure in the absence of abnormal grain growth mainly presents excellent wear resistance. Without wishing to be bound by theory, it is presently believed that one of the reasons for the unexpected improvement is based on the formation of sub-grain boundaries within the ZrO₂ grains due to piled up dislocations, which play a role in imaginary dividing the ZrO₂ grains into more finer sized grains.

That is, when fine Al₂O₃ grains of the second phase are dispersed within the ZrO₂ grains of the first phase, a residual stress field is locally generated around each of fine Al₂O₃ grains dispersed within the ZrO₂ grains by a difference in thermal expansion coefficient between Al₂O₃ and ZrO₂ during a cooling procedure after sintering. By the influence of this residual stress field, lots of dislocations occur within the respective ZrO₂ grains. The dislocations are then piled up with each other, and finally the sub-grain boundaries are formed. The sub-grain boundaries provide the finer-grained structure, which has the capability of increasing a critical stress required for causing the stress-induced phase transformation from the tetragonal ZrO₂ to the monoclinic ZrO₂. As a result, the composite ceramic material of the present invention demonstrates high mechanical strength and toughness as well as excellent wear resistance and hardness.

Therefore, the additive amounts of Y₂O₃ and CeO₂ defined in the present invention were determined to prevent the low temperature degradation, and also achieve the appropriate grain growth of the ZrO₂ grains required to the formation of the “nano-composite structure” to improve mechanical strength and toughness of the composite ceramic material.

The composite ceramic material of the present invention is particularly suitable for applications needing wear resistance. For example, it is preferred to use the composite ceramic material of the present invention for an artificial joint described in the International Publication WO 02/11780A1. That is, when a joint portion of the artificial joint is provided by a sliding contact between the composite ceramic material and polyethylene, it is possible to remarkably reduce a wear amount of polyethylene. In addition, when the joint portion of the artificial joint is provided by a sliding contact between the composite ceramic materials, excellent wear resistance can be achieved. Thus, the use of the composite ceramic material of the present invention is useful to obtain the artificial joint having the capability of stably providing a smooth joint motion for an extended time period under severe in-vivo conditions.

Next, the method of producing the ZrO₂—Al₂O₃ composite ceramic material of the present invention is explained in detail. This production method comprises the steps of preparing a first ingredient for providing the ZrO₂ grains of the first phase and a second ingredient for providing the Al₂O₃ grains of the second phase, mixing the first ingredient with the second ingredient such that a content of the second phase in the composite ceramic material is in the range of 20 to 60 vol %, and more preferably 30 to 50 vol %, molding a resultant mixture in a desired shape to obtain a green compact, and sintering the green compact at a required sintering temperature in an oxygen-containing atmosphere.

The first ingredient is prepared such that the CeO₂ and Y₂O₃ contents in the first phase of the composite ceramic material are in the ranges of 10 to 12 mol % and 0.005 to less than 0.5 mol %, respectively, and the first phase is composed of 90 vol % or more of tetragonal ZrO₂. For example, as the first ingredient, it is preferred to use a tetragonal ZrO₂ powder obtained by allowing ZrO₂ to form a sold solution with the above-defined amounts of CeO₂ and Y₂O₃.

Alternatively, the tetragonal ZrO₂ powder may be prepared by the following method. That is, a cerium containing compound such as cerium salts and a yttrium containing compound such as yttrium salts are added to an aqueous solution of a zirconium salt. Then, hydrolysis is performed by adding an alkali aqueous solution such as aqueous ammonia to a resultant mixture solution to obtain a precipitate. The precipitate is dried, calcined in the oxygen-containing atmosphere, e.g., in the air, and then pulverized by means of wet ball milling to obtain the tetragonal ZrO₂ powder having a desired particle distribution

The second ingredient is prepared such that Al₂O₃ grains are dispersed in the composite ceramic material after sintering. For example, it is preferred to prepare the Al₂O₃ powder having a desired particle distribution by adding an alkali aqueous solution such as aqueous ammonia to an aqueous solution of an aluminum salt to perform hydrolysis, drying a resultant precipitate, calcining the precipitate in the oxygen-containing atmosphere, e.g., in the air, and pulverizing the calcined precipitate by means of wet ball milling. Alternatively, a marketed Al₂O₃ powder may be used.

It is preferred to perform the sintering step at a sintering temperature of 1400 to 1500° C. in the oxygen containing atmosphere. In the sintering step, it is important to satisfy the conditions that the average grain sizes of the ZrO₂ grains of the first phase and the Al₂O₃ grains of the second phase are in the ranges of 0.1 to 0.8 μm, and 0.1 to 0.5 μm, respectively. More preferably, the sintering condition is determined such that the ratio of the number of the Al₂O₃ grains dispersed within the ZrO₂ grains relative to the number of the entire Al₂O₃ grains dispersed in the composite ceramic material is 2% or more.

By the way, a mobility of grain boundary that is an index for sintering is much higher in the Ce-TZP ceramic containing CeO₂ as the stabilizer than the Y-TZP or alumina ceramic. Therefore, the composite ceramic material containing the Ce-TZP ceramic can be densely sintered by means of pressureless sintering without using pressure sintering or a HIP (hot isostatic pressing) treatment. However, the HIP treatment may be performed in the oxygen-containing atmosphere after sintering, if necessary. To obtain the effects of the HIP treatment at the maximum, it is preferred that the sintered body of the composite ceramic material obtained by the sintering step has a relative density of 95% or more. A concentration of oxygen in the oxygen-containing atmosphere in the sintering step is not specifically limited. A mixture gas of oxygen and an inert gas such as argon may be used. In this case, it is preferred that the concentration of oxygen is approximately 5 vol % or more with respect to a total volume of the mixture gas.

EXAMPLES

Preferred examples of the present invention are explained below. However, needless to say, the present invention is not limited to these examples.

Examples 1 to 20 and Comparative Examples 1 to 5

A ZrO₂—Al₂O₃ composite ceramic material of each of Examples 1 to 20 was produced by the following method. That is, as the first ingredient for providing ZrO₂ grains that are the first phase of the composite ceramic material, a tetragonal ZrO₂ powder having a specific surface of 15 m²/g and containing required amounts of CeO₂ and Y₂O₃ listed in Table 1 or 2 was used. On the other hand, as a second ingredient for providing Al₂O₃ grains that are the second phase of the composite ceramic material, an α-Al₂O₃ powder having an average particle size of 0.2 μm was used.

Next, a required amount of the α-Al₂O₃ powder listed in Tables 1 and 2 was added to the tetragonal ZrO₂ powder, and then mixed in ethanol for 24 hours by means of wet ball milling. A resultant mixture was dried to obtain a mixed powder. The mixed powder was molded at the pressure of 10 MPa by uniaxial pressing with a die having a diameter of about 68 mm to obtain a disk-shaped green compact. Next, a CIP (cold isostatic pressing) treatment was performed to the green compact at the pressure of 147 MPa. Finally, the green compact was sintered at the sintering temperature of 1450° C. for 2 hours in the air by pressureless sintering to obtain a sintering body.

The ZrO₂—Al₂O₃ composite ceramic material of Comparative Example 1 was produced by the same method as Example 1 except that Y₂O₃ was not added. The ZrO₂—Al₂O₃ composite ceramic material of Comparative Example 2 was produced by the same method as Example 1 except for the addition of 1 mol % of Y₂O₃. In addition, the ZrO₂—Al₂O₃ composite ceramic materials of Comparative Examples 3 to 5 were produced by the same method as Example 1 except that the Al₂O₃ content is out of the range of the present invention, as listed in Table 2.

With respect to each of Examples 1 to 20 and Comparative Examples 1 to 5, the sintered body has a relative density of more than 99%. From results of X-ray diffraction analysis, it was confirmed that the first phase of the respective sintered body is composed of more than 95 vol % of tetragonal ZrO₂ and the balance of monoclinic ZrO₂. There was no X-ray profile showing the presence of cubic ZrO₂. From the SEM (scanning electron microscope) and TEM (transmission electron microscope) observations of the sintered body, it was confirmed that the sintered body has a nano-composite structure characterized in that fine Al₂O₃ grains of the second phase are dispersed within the ZrO₂ grains of the first phase.

As listed in Tables 1 and 2, average grain sizes of the first and second phases of the sintered body measured from the SEM and TEM observations are respectively in the ranges of 0.3 to 0.8 μm, and 0.2 to 0.5 μm. Moreover, to evaluate mechanical properties of the composite ceramic material, test specimens having the dimensions of 4 mm×3 mm×40 mm were prepared from the sintered body. Subsequently, 3-point bending strength and fracture toughness were measured at room temperature by use of the test specimens. The fracture toughness was determined by the IF method. Results are listed in Tables 3 and 4.

In addition, an Al₂O₃ dispersion ratio (W1), which is defined as a ratio of the number of the Al₂O₃ grains dispersed within the ZrO₂ grains relative to the number of the entire Al₂O₃ grains dispersed in the composite ceramic material, and a ZrO₂ dispersion ratio (W2), which is defined as a ratio of the number of the ZrO₂ grains that are two or more times larger than the average grain size of the first phase relative to the number of the entire ZrO₂ grains dispersed in the composite ceramic material, were determined by the following method. First, a sample was prepared by polishing and heat-treating the sintered body. Then, the SEM or TEM observations of the sample was performed to counting the number (S1) of entire Al₂O₃ grains of the second phase within a view field, the number (n1) of fine Al₂O₃ grains dispersed in the ZrO₂ grains of the first phase within the same view field, the number (S2) of the entire ZrO₂ grains of the first phase within the same view field, and the number (n2) of the ZrO₂ grains that are two or more times larger than the average grain size of the first phase within the same view field. By substituting these values to the following equations, the Al₂O₃ and ZrO₂ dispersion ratios were calculated. Results are shown in Tables 3 and 4. W1 [%]=(n1/S1)×100, W2 [%]=(n2/S2)×100.

With respect to each of Examples 1 to 15 and Comparative Examples 1 and 2, an autoclave test was performed to check the presence or absence of low temperature degradation of the composite ceramic material. That is, after the autoclave test was performed for 100 hours under a severe condition of 121° C. and 1.15 MPa, a monoclinic ZrO₂ amount was measured, and then compared with the monoclinic ZrO₂ amount measured before the test. Results are shown in Table 3.

With respect to all of Examples, as shown in Tables 1 and 2, the Al₂O₃ dispersion ratio W1 is more than 2%, and the ZrO₂ dispersion ratio W2 is less than 10%. In addition, no significant phase transition of tetragonal ZrO₂ to the monoclinic ZrO₂ by the autoclave test was observed.

In Comparative Example 1, the ZrO₂ dispersion ratio W2 is 15%. It is thought that this increase in the ZrO₂ dispersion ratio W2 is associated with a considerable decrease in bending strength. In Comparative Example 2, the amount of the monoclinic ZrO₂ increased from 1.8 vol % to 25 vol % by the autoclave test. It is thought that this increase in the monoclinic-ZrO₂ amount is associated with a considerable decrease in fracture toughness. In comparative Examples 3 and 4, since the Al₂O₃ content in composite ceramic material is less than 20 vol %, the effect of preventing the grain growth of ZrO₂ was not enough, and the bending strength lowered. On the other hand, in Comparative Example 5, the bending strength considerably lowered because the Al₂O₃ content is more than 60 vol %.

As understood from the Examples described above, the ZrO₂—Al₂O₃ composite ceramic material of the present invention characterized by using 10 to 12 mol % of CeO₂ as the stabilizer in combination with the extremely small amount (0.005 to less than 0.5 mol %) of Y₂O₃ simultaneously prevents both of a decrease in bending strength caused by the abnormal grain growth of ZrO₂ that is a major disadvantage of the Ce-TZP ceramic, and the phase transformation to monoclinic ZrO₂ closely associated with low temperature degradation that is a major disadvantage of the Y-TZP ceramic, to demonstrate excellent mechanical strength and toughness.

Therefore, it is expected that the composite ceramic material of the present invention is widely utilized in various application fields, for example, parts for industrial machine such as ferrules for optical fiber connector, bearings and dies, cutting tools such as scissors and saw blades, stationery goods, chemical goods such as mechanical seals and miling media, goods for sport, medical equipments such as surgical knives, biomaterial parts such as artificial joint, artificial bone, artificial dental root, abutment and crown.

TABLE 1 Composite Ceramic Starting Material Material First Phase Average Grain (mol %) Second Phase (vol %) Size (μm) CeO₂ Y₂O₃ Al₂O₃ ZrO₂ Al₂O₃ EXAMPLE 1 10 0.020 30 0.69 0.38 EXAMPLE 2 10 0.030 30 0.63 0.35 EXAMPLE 3 10 0.170 30 0.45 0.31 EXAMPLE 4 10 0.330 30 0.39 0.27 EXAMPLE 5 10 0.470 30 0.37 0.30 EXAMPLE 6 11 0.010 30 0.73 0.40 EXAMPLE 7 11 0.070 30 0.55 0.30 EXAMPLE 8 11 0.300 30 0.40 0.27 EXAMPLE 9 11 0.370 30 0.39 0.27 EXAMPLE 10 11 0.430 30 0.38 0.30 EXAMPLE 11 12 0.005 30 0.78 0.43 EXAMPLE 12 12 0.100 30 0.50 0.30 EXAMPLE 13 12 0.230 30 0.42 0.27 EXAMPLE 14 12 0.400 30 0.38 0.27 EXAMPLE 15 12 0.490 30 0.37 0.30 COMPARATIVE EXAMPLE 1 10 0 30 1.00 0.38 COMPARATIVE EXAMPLE 2 12 1.000 30 0.35 0.28

TABLE 2 Composite Ceramic Starting Material Material First Phase Average Grain (mol %) Second Phase (vol %) Size (μm) CeO₂ Y₂O₃ Al₂O₃ ZrO₂ Al₂O₃ COMPARATIVE EXAMPLE 3 10 0.45 0 2.50 — COMPARATIVE EXAMPLE 4 10 0.45 10 1.00 0.25 EXAMPLE 16 10 0.45 20 0.58 0.26 EXAMPLE 17 10 0.45 30 0.35 0.28 EXAMPLE 18 10 0.45 40 0.32 0.29 EXAMPLE 19 10 0.45 50 0.29 0.30 EXAMPLE 20 10 0.45 60 0.27 0.31 COMPARATIVE EXAMPLE 5 10 0.45 70 0.26 0.32

TABLE 3 Autoclave Test: Fracture Al₂O₃ Amounts of Monoclinic 3-point Bending Toughness Dispersion ZrO₂ Dispersion ZrO₂ (vol %) Strength (MPa) (MPa · m^(1/2)) Ratio W1 (%) Ratio W2 (%) Before Test After Test EXAMPLE 1 1050 18.8 3.4 7.8 4.1 4.2 EXAMPLE 2 1100 18.6 3.1 7.0 3.8 3.7 EXAMPLE 3 1240 18.4 3.3 4.2 3.6 3.7 EXAMPLE 4 1290 18.2 3.1 2.5 4.2 4.1 EXAMPLE 5 1280 18.0 2.5 2.1 3.9 4.0 EXAMPLE 6 1120 15.5 3.3 8.5 3.1 3.2 EXAMPLE 7 1230 15.4 3.0 6.0 2.9 2.8 EXAMPLE 8 1330 15.2 3.2 2.7 3.3 3.5 EXAMPLE 9 1310 15.0 3.1 2.4 3.4 3.3 EXAMPLE 10 1290 14.8 2.6 2.2 3.2 3.1 EXAMPLE 11 1200 11.5 3.2 9.3 2.6 2.5 EXAMPLE 12 1350 11.3 3.1 5.0 2.9 2.8 EXAMPLE 13 1400 11.2 3.2 3.2 2.3 2.5 EXAMPLE 14 1400 11.1 3.1 2.3 2.7 2.8 EXAMPLE 15 1450 11.1 2.5 2.0 2.8 2.6 COMPARATIVE 950 18.9 3.6 15.0 3.6 3.7 EXAMPLE 1 COMPARATIVE 1300 8.5 2.5 1.8 1.8 25.0 EXAMPLE 2

TABLE 4 3-point Bending Fracture Al₂O₃ ZrO₂ Strength Toughness Dispersion Dispersion (MPa) (MPa · m^(1/2)) Ratio W1(%) Ratio W2(%) COMPARATIVE 700 23.0 — 25.2 EXAMPLE 3 COMPARATIVE 1010 22.3 3.0 13.3 EXAMPLE 4 EXAMPLE 16 1170 21.0 2.9 4.8 EXAMPLE 17 1290 18.9 2.8 2.1 EXAMPLE 18 1340 16.0 2.6 1.8 EXAMPLE 19 1270 12.5 2.3 1.6 EXAMPLE 20 1100 8.5 2.1 1.5 COMPARATIVE 750 4.5 1.4 1.3 EXAMPLE 5 

1. A ZrO₂—Al₂O₃ composite ceramic material comprising: a first phase of ZrO₂ grains having an average grain size of 0.1 to 0.8 μm, and comprising 10 to 12 mol % of CeO₂ and 0.005 mol % to 0.17 mol % of Y₂O₃, said ZrO₂ grains composed of 90 vol % or more of tetragonal ZrO₂; and a second phase of Al₂O₃ grains having an average grain size of 0.1 to 0.5 μm, a content of said second phase in the composite ceramic material being in a range of 20 to 60 vol %.
 2. The composite ceramic material as set forth in claim 1, wherein a content of said second phase in the composite ceramic material is in a range of 30 to 50 vol %.
 3. The composite ceramic material as set forth in claim 1, wherein a ratio of the number of said Al₂O₃ grains dispersed within said ZrO₂ grains relative to the number of the entire Al₂O₃ grains dispersed in the composite ceramic material is 0.02 or more.
 4. The composite ceramic material as set forth in claim 1, wherein a ratio of the number of said ZrO₂ grains that are two or more times larger than the average grain size of said first phase relative to the number of the entire ZrO₂ grains dispersed in the composite ceramic material is 0.10 or less.
 5. A ZrO₂—Al₂O₃ composite ceramic material as claimed in claim 1, wherein said first phase comprises 10 to 12 mol % of CeO₂ and 0.005 mol % to 0.100 mol % of Y₂O₃.
 6. A ZrO₂—Al₂O₃ composite ceramic material as claimed in claim 1, wherein said first phase comprises 10 to 12 mol % of CeO₂ and 0.005 mol % to 0.070 mol % of Y₂O₃.
 7. A ZrO₂—Al₂O3 composite ceramic material as claimed in claim 1, wherein said first phase comprises 10 to 12 mol % of CeO₂ and 0.005 mol % to 0.030 mol % of Y₂O₃.
 8. A ZrO₂—Al₂O₃ composite ceramic material as claimed in claim 1, wherein said ZrO₂ grains are composed of more than 95 vol % of tetragonal ZrO₂ with a balance of monoclinic ZrO₂.
 9. A ZrO₂—Al₂O₃ composite ceramic material as claimed in claim 2, wherein said ZrO₂ grains are composed of more than 95 vol % of tetragonal ZrO₂ with a balance of monoclinic ZrO₂.
 10. A ZrO₂—Al₂O₃ composite ceramic material as claimed in claim 3, wherein said ZrO₂ grains are composed of more than 95 vol % of tetragonal ZrO₂ with a balance of monoclinic ZrO₂.
 11. A ZrO₂—Al₂O₃ composite ceramic material as claimed in claim 4, wherein said ZrO₂ grains are composed of more than 95 vol % of tetragonal ZrO₂ with a balance of monoclinic ZrO₂.
 12. A ZrO₂—Al₂O₃ composite ceramic material as claimed in claim 5, wherein said ZrO₂ grains are composed of more than 95 vol % of tetragonal ZrO₂ with a balance of monoclinic ZrO₂.
 13. A ZrO₂—Al₂O₃ composite ceramic material as claimed in claim 6, wherein said ZrO₂ grains are composed of more than 95 vol % of tetragonal ZrO₂ with a balance of monoclinic ZrO₂.
 14. A ZrO₂—Al₂O₃ composite ceramic material as claimed in claim 7, wherein said ZrO₂ grains are composed of more than 95 vol % of tetragonal ZrO₂ with a balance of monoclinic ZrO₂.
 15. A ZrO₂—Al₂O₃ composite ceramic material as set forth in claim 1, wherein a content of said second phase in the composite ceramic material is in a range of 30 to 50 vol %, wherein said Al₂O₃ grains have an average grain size of 0.26 to 0.40 μm, wherein said ZrO₂ grains are composed of more than 95 vol % of tetragonal ZrO₂ with a balance of monoclinic ZrO₂, and wherein said ZrO₂ grains have an average grain size of 0.27 to 0.73 μm.
 16. A ZrO₂—Al₂O₃ composite ceramic material as set forth in claim 3, wherein a content of said second phase in the composite ceramic material is in a range of 30 to 50 vol %, wherein said Al₂O₃ grains have an average grain size of 0.26 to 0.40 μm, wherein said ZrO₂ grains are composed of more than 95 vol % of tetragonal ZrO₂ with a balance of monoclinic ZrO₂, and wherein said ZrO₂ grains have an average grain size of 0.27 to 0.73 μm.
 17. A ZrO₂—Al₂O₃ composite ceramic material as set forth in claim 4, wherein a content of said second phase in the composite ceramic material is in a range of 30 to 50 vol %, wherein said Al₂O₃ grains have an average grain size of 0.26 to 0.40 μm, wherein said ZrO₂ grains are composed of more than 95 vol % of tetragonal ZrO₂ with a balance of monoclinic ZrO₂, and wherein said ZrO₂ grains have an average grain size of 0.27 to 0.73 μm.
 18. A ZrO₂—Al₂O₃ composite ceramic material as set forth in claim 5, wherein a content of said second phase in the composite ceramic material is in a range of 30 to 50 vol %, wherein said Al₂O₃ grains have an average grain size of 0.26 to 0.40 μm, wherein said ZrO₂ grains are composed of more than 95 vol % of tetragonal ZrO₂ with a balance of monoclinic ZrO₂, and wherein said ZrO₂ grains have an average grain size of 0.27 to 0.73 μm.
 19. A ZrO₂—Al₂O₃ composite ceramic material as set forth in claim 6, wherein a content of said second phase in the composite ceramic material is in a range of 30 to 50 vol %, wherein said Al₂O₃ grains have an average grain size of 0.26 to 0.40 μm, wherein said ZrO₂ grains are composed of more than 95 vol % of tetragonal ZrO₂ with a balance of monoclinic ZrO₂, and wherein said ZrO₂ grains have an average grain size of 0.27 to 0.73 μm.
 20. A ZrO₂—Al₂O3 composite ceramic material as set forth in claim 7, wherein a content of said second phase in the composite ceramic material is in a range of 30 to 50 vol %, wherein said Al₂O₃ grains have an average grain size of 0.26 to 0.40 μm, wherein said ZrO₂ grains are composed of more than 95 vol % of tetragonal ZrO₂ with a balance of monoclinic ZrO₂, and wherein said ZrO₂ grains have an average grain size of 0.27 to 0.73 μm. 